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“LUBRICATION OIL EMULSIONS” 


BY 


DOUGLAS IRVING MAXWELL 


THESIS 
a ChE 
DEGREE OF BACHELOR OF SCIENCE 
ree 


1 


CHEMICAL ENGINEERING 


' 


COLLEGE OF Lara ARTS AND SCIENCES 
UNIVERSITY OF ILLINOIS 


1922 


Digitized by the Internet Archive 
in 2015 


https://archive.org/details/lubricationoilemOOmaxw 


UNIVERSITY OF ILLINOIS 


Instructor in Charge 


APPROVED :_< 


SCT laG, HEAD OF DEPARTMENT OF -@HBMISORY. .._......_._..._=._-.._- 


ACKNO WLEDG AN ENT 


The writer wishes to express 
his thanks and appreciation to Pr. 
T. & Layng for nis assistance in 
this work. ‘ihe problem was suggeste 
ed by him, and the work was done 


under his direction. 


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Table of Contents 


intro duction 

Theo retical 

Experimental 

biseussion and conclusion 


Bibliography 


Page 1 
Page 2 


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Page 13 
Page 15 


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LUBRICATION OL1L SNULSIONS 


The subject of emulsions has been one of interest to 
the chemist for the past twenty yeers. iiany theories have been 
advanced as to the cause of the phenomena of emulsification, 
but they were specific and not general in their application. 

A great deal of work has been done on the subject, each worker 
dealing with some particular phase of the subject thet inter- 
ested him most. “ As a. result e mass of arbitrery data has ace 
cumulated which has a bearing uvon aimost eny ctestion that 
might arise. 

In the petroleum industry the handling ef esuisions 
and their subsequent breaking up is often a troublesome and 
expensive operation. cuften the crudé oil appears at the sure 


face as an emulsion, waiie in refinery prectice the care and 


means taken to prevent its formation and tie equipment for 
handling emulsions form quite an itea in plant expense. 
Yecognizing two types of emulsions with which the pee 
troleum chemist has to deal, (1) crude oil emulsions, and (2) 
refined oil enulsions, this work was undertsken in an attempt 
to try and find out some of the characteristics of lubricating 
oils when emulsified, the cause, and if possible, 2 means by 
which an emulsion of Lubricating oil with water could be pre- 
vented fron forming. <A great quantity of wrk has been done 
on how to make, or form, permanent enulsions, but the litera- 
ture contains but few references as to the prevention of them. 


This work deals with the prevention of the formetion of emule 


sions with «= refined oil in water. 


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Por a brief review of the literature of emulsions A. W. 


Thomas (1) has done some valuable work. ‘this article states 


that an emulsion is a heterogeneous system consisting of one 


liquid dispersed as tiny droplets in another liquid. It has 


been definitely established thet three phases are eseential for 


the formation of a stable emulsion: (1) Liquid A, (2) Liquid B, 


and (3) an emulsifying agent. ‘The two liquids must be immis- 


sible, or nearly so, in one another. The two main types of 


water censtitutes one of the lie 


emulsions are those wherein 


quid phases, and two main types are recognized: (1) a liquid 


(oil) dispersed in water, and (2) water dispersed in oil. The 


@,, wiether 


factor which contrels tne tyne of emulsion, i. 


water or oii is the external phse, is the nature of the enule 


sifying agent. 


In general, if the emulsifying azent is more easily 


wetted by water than by oil, then water will be the external 


Phese end oil the dispersed phase, while if the emulsifier is 


more eesily wetted by tne oil, the reverse will be trues. Bane 


croft '2' puts it this way: If the surface tension between 


Liquid A end the emulsifying agent is lower than the surfsce 


tension betwee Liquid 8 and the euulsifying agent, Liquid A 


will be the disversing and Liguid B the dispersed phase. Since 


the emulsifying agent is almost slways recognized as a colloidal 


substance, it is fairly safe to say tnat a hydrophile colloid as 


and emulsifying agent will emulsify oil in water and a hydroe 


phobe colloid will emulsify water in oil. ‘This latter state~ 


ment is subject to modification, nowever, which will be conside 


ered later. 


«3 

There is a very simple and reliable method of determining 
the type of emulsion. Upen the addition of an emulsion of oile- 
inewater (1. e, oil the dispersed phase) to water, it will dis- 
perse. Similarly, a watereineoil emulsion will mix with oil. 
In short, an enulsion will freely mix or dilute with more of its 
external phase, but not with more of its intemal phase. 

QOii In Water Haulsions 

There are three main classes of this type ef emulsions: 
(1) The emulsifying agent is an electrical charge on the oil 
particles, provably due to selective adsorption of the OH» ion 
of the water by the oil particles. 
(2) The emulsifying agent is a wateresoluble colloid. 
(3) The emulsifying agent is an insoluble, or very siightly sole 


uble colloid. 


there are many ceases also where a combination of two or 


even three of the above may function as emulsification agents. 

{1) @lectriecal Charge as Bmulsifying Agent--These emule 
Sions are the simplest. ‘hey are identical with those observed 
in the condensate from stema engines. ‘They may be prepared in 
three ways '3'. 

(a) By shaking a small amount of mineral oil (2 cc.) with 
a larger volume of water (100 Ge. ) for 48 hours. 

(ob) By boiling a drop of mineral oil with excess water 
under a reflux condenser for 30 kours. 

(c) Waoen a small amount of mineral oil dissolved in ale 
cohol is poured into water an emulsion results imnediately. 

Lewis found the size of the perticles in these enuulsions 


to be alike no matter cow made, and of tne order of 0.4 micron. 


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They are negatively charged, the potential difference of the 
double layer (lielmholtz effect) being «0.05 volt. iis measures 
ment of the size of the charge on the droplet, by electrophoresis | 
method, indicated 4.4 x 10«7 electrostatic units. These emule | 
Sions owe their stability to the electrical charge end Brownian 
novement . 

‘The origin of this electrical charge is obscure. Eliis 
'4’ ascribed it to difference in dislectriec constants, sccording 
to the rule of Coehn thet a substance of high dielectric constant 
is positive to one of a lower dielectric constant when one is 
dispersed in the other. This, te be sure, does not explain. He 
prepared mineral oil enulsions by the shaking method and obtained 
a concentration of one part oil in 10,000 parts of water, the 
size of the particles being 1 to 2 microns in diameter, and the 
specific conductivity of the emulsion was 18 x 10«6 mhos. He 
found the potential of the double layer to be «0.05 volt, as 
Lewis did; but his measurement of electrical charge showed 2.12 
x 10-6 electrostatic wits for the lemicron particles. He also 
noted that they were most stable in the presence of n/l000 sod- 
ium hydroxide. ile ascribed the stability of this type entirely 
to the electrical charge and stated that surfece tention had 
nothing to do with it. 

Hetschek '5' suggested that the stability of such miner- 
al oil emulsions might be due to the fact that the specific 
gravities of the phases were close to esch other, but Groschief 
'6" contested this view. 

Powers *7’ prepared this type of eiulsion by the shaking 
method and determined the double layer potential to be -0.046 


« 


volt, which checks fairly well with Lewis and fllis. ile studied 


the effeet of the addition of electrolytes to the emulsion and 
noted that anions have tie powers to inerease this negative 
potential, while cations decrease it. Very small amounts of Kel 
and KgFe{ en) 6 (up to 0.001 molayv) inereased it, while lerger 
anounts decreased it. Galts with polyvalent cations always dee 
creased it, due to the predominating positive charge of the 
cations over the anions. He noted later that while an imuediate 
sharp change in the contact potential occurred upon the addition 
ef salt, there always ensued a secondary slower change; in tie | 
ease Of & Salt like saclg the change is continuous in the same | 
sense, whereas in cases like ‘Lel3. it reverts back a little, 

due to ieoss of Alesse on account of nydroliysis. 

(2) Wateresoluble colloid as Snulsifying Agent--Good 
emulsifiers of this class are sodium and potassium SOPPS, ess 
albusen, Selatin, ete. The emulsions wherein sony is the emul- 
gifying szgent will be the only ones taken up. 

Previous te 1899, Neoh was classified aw a1 excellent 
emulsifying agent for fatty oils in water, Donnan's '8' investi- 
gation showed that its euulsifying powers were resily due to the 
soap formed by the interaction with the small amount of free 
fatty ecid that is always found in fatty oils. 

In 1907 Pickering '9' did some notable work upon emulsions. 
in all of his experiments he eaulseified a paraffin oil in weter, 
by pwaping it back and forth through a rose nozzle garden syringe 
He found potash soaps to be better than sodium soaps as euulsi- 
filers and noted that « eertain eritical concentration of soap 


was required for each proportion of oil and water, @. ge, to 


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emulsify 75 volumes of oil with 25 volwaes of water, the latter 
must contain 0.7 te 1.8 per cent of potash soap, or 40 volumes 
ef coil to 60 volumes of water, 0.3 to 25.0 per cent soap can be 
used. 

He noted that seaps vary greatiy in emulsifying power, 
some brands heing useless, and, in fact, tw batches of the same 
brand mey vary in enulsifying powers He noted also thet while 
rise in temperature facilitated emulsification, it had no influe 
ence on the compo sition. 

{3) Insoluble, or only siightiy soluble, colloid as enule 
sifying agente«~There are a number of basic metallia salts thst 1. 
act a® excellent emulsifiers. Pickering '10° states that while 
viscosity and low surface tension of sa liquid facilitates the 
emulesifiestion of an oil in it, yet it is possible to make an 
emulsion in s liauid which does not possess these properties. 

The wost important condition is the presence of svall particles 
insoluble in the dispersion mediwa which coat over the oil partie 
eles and prevent then from cofiesecing. In order that such pertieg 
cles have the power to form emulsions they must show only a 
slight tendency to unite with one another, must be readily wetted 
by water and must not be crystalline. 

Weter in 0i1 Hmulsions 

This type of amulsion is common in lubricating greases 
and is easily produced with the aid of calcium end maygnesiwn 


soaps. Clowes ‘11* performed some striking experiments with 
soap enulegion of olive oil and water. Sy addition of calcium 


chloride to an emulsion of oil in water (with sedium oleate as 


emvisifying agent), he found that when the calciwn concentration 


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exceeds the chemical equivalence to sodiun, the emulsion passes 
threugh a eritieal point and changes to one of the water dis+ 
persed in oil type. He found that sodiusa, potassius, and lithum 
soaps emulsify oil in weter while magnesiua, strontiwa, barium, 
iron and aluainwa soaps emulsify water in oii. ile expinined this 
pienomena by the fact that the alkali soaps are watted more by 
weter than by oll and since it is thought that the surface tere 
sion is lower en the water side then on the oil side of the 
globules, the films will bend eonvex te the water and concave 

te the cil, enveloping the oil particles, because the ares of 
tae inner surface cf a spheres is less than thet of tie Guter cure 
face. Similar reasoning helds for the dispersion of weter in 
oil by the cither soaps mentioned. 

Lengmuir '12' has e very interesting theory as to the cause 
of emulsions, Ue starts with the view point thst ali the forces 
inve.ved in the structure of solids and liquids are really cheme 
ical in neture, end taat not only cheaical combination, but 
aleg the phenowena cf condensation, evaporation, adsorption, co 
besion, avyetaldiaition, liquifsaction, viscosity, surfvace tension, 
etc., are wonifestations of either primary or secondary valence 
(Werner), the conclusion is reached thet adsorbed films on plane 
surfaces of solids or liguids should in general be one otom or 
one group wele in thickness. The experiments of Devaux, Raleigh, 
Wercelin, and Peckels have show that very small amounts of 
certain cile on the surfece of water have no appreciable effect 
ou its surfact tensien, but that the surfact tension begins to 
decrease suddenly when the asount of o41 per wmit area is ine 


creaged beyond a certain sharp limit. This result leads to the 


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conciusion that the amount of oil necessary to affect surface 
tension corresponds to a layer one mole in thickness. Jurthermore, 
Langmuir reagons that since the oli spreads on water and since 
the presence of »COOH, -CO, or «UH groups in an organic mole 
terids to render a substance soluble in water (thus indicating a 
strong affinity of water for -GOUH, ete.), we must regard the 
“COOH groups in the oil film as chemically combined with the 
adjecent liz70 molecules and that therefore the oil film consists 
of oil molecules standing on end, the =COOH groups being next the 
water and the hydrocarbon chain extending upwards from the sure 
face. Pure hydrocarbon chains do not spresd upon the surfece of 
water. Thus, when an oil spreads upon water it is an inaication 
thet a soluble group is present in the hydrocarbon chain. 

rem the forezoing resume it is readily seen thet the lite 


erature on emulsions is e collection of aata on specific problems 


that may have @ general appiication, and maybe not, most of it 
has an indirect bearing upon the subject as oe whole. 
Some of the means used to break up emulsions are: 
i- Addition of excess of dispersed phase. 


é- Addition of a Liquid in which the two 
Liquid phases are soluble. 


Pestruction of the enulsifying agent. 
Filtration, 

Heating. 

HreeZzing. 

HLeetrolyzing. 

Jent ri fuging. 


In this work 211 emulsions were broken up by impinging 


upon a hot plate. 


Hi ae ibid dah 
prereset 
SH gulag eae 


* 


uxperimental 

In reviewing the literature two theories were selected 
that appeared to have the most bearing upon this problem. They 
are’ 

(1) Bleetrical charge on the droplet. 

(2) Water soluble group in the chain. 

vith the abeve two theories in mind it was necessary to 
procure en oil that could be used as a blank test oii. An oil 
with a sireaight pereffin chain structure thet had not been come 
pounded with any other oil or a fatty acid was found in Nujol, 
whieh responded with a demulsification number of 1080 out of a 
possible 1200 for 2 meximun. ‘heat little emulsification there 
was was due to the electrical charge on the particle and could 
be dissipated by adding a little water. 

The Bureau of Standards' method for deternining the demule 
sification number was used. It consists in taxing 27 ee. of 
ofl and 53 ce. of water in a 100 ce. graduate cylinder, stir 
with a paddle rotating at 1500 % FP. ‘4. for five minutes, keepe- 
ing the temperature at 55° c. A record is kept of the number of 
ce, of 011 that settles out. This number times 60 divided by 
tie nunber of minutes taken in the settling out is the demulsie 
fication number. 

Rxample: 


Sable Nos 1 
Min, efter stopping pneddle-«---cc. of oil settled outeweuJo, 


, hee 60. 
5, 6. 92. 
10. 10. 60. 


The maximum rate of settling is taken as the demulsification 


number, in the above case tue number would be 72. ‘nus an oil 


+~ 10 « 
that was 100% demulsifiable would have its 23 ec. of oil settle 
out in the first minute after stopving the paddle. 
Upon running a number on Havoline B it gave a demulsifics- 


tion number of 52.5. Am analysis of the oil proved it to be a 


compounded oil and that it contained 1.42% of fetty acid. To 


this fatty acid might be attributed the low demulsification 
number, This was partly proven by adding 1.21% of stearic acid 
to Nujol waich reduced its number from 1080 to 275. Havoline 
being a eonpounded oil was found wnsuiteble for this werk. 

In leoking for 2 commercial oil suitable for the work Polar. 
ine No. 2 was selected. it is a straight Pire dietilled paraffin 
bese oil «nd should give 9 high demulsification number. ‘The nume 
ber was found te be zero. it was now a question of finding the 


cause of the emulsification. er fear tneat the oil had not been 


sufficiently refined it wes treated with varying proportions of 
concentrated sulfuric acid at different tenperatures. lione cf the 
trentiments had any appreciable eifect on the demulsification nun» 
ber. 

Treatment with liquid sulfur dioxide at «10° C. and subsee 
quent thorough washing failed to produce any results along the 
Gesired line. 

‘aking into account Langnuir's soiuble group theory it was 
decided to treat the oil with various chemicals to try and de- 
stiroy the soluble group or reicer it leas active as a cause of 


emulsification. All of the salts used had a high solubility in 
water. 


In each case the oil wes agitated with the metallic salt 


for thirty minutes at a temperature of 120° C. ‘She oii was then 


a 


H 
‘ 1 


» il e 


given a thorough washing and filtered through fuller's earth that 
had just been remeved from » crucible where the temperoture was 
around 300° Gg, 

The results from the various trentments are tabulated below 


in Table iI. 


Table It 
Ant. oil Chemical Pemul, No. 
500 ea. 1/8 lo. anelg 25-6 
256 ce. 25 gr. Culno) 6. 
500 ce. 20% Vol. Babs anel, Sole 0. 
250 cee 25 E¥. Alo(sc) Oo, 
250 ce. 25 gr. Wiely,6 ig 0. 
150 ec. 15 gr. Cael, 66. 
150 ce. 15 gr. Beod Oe 
150 ce. 1 gr. Cacis 0. 
150 ce. 26 gr. unel5 O. 
150 CGe 22 2s Sachs a. 
150 ec. 16 gr. Zno O. 
i50 ea. i, ogy. Ca} 0. 
199 GG. & ihe Caw, 4H,0 QO. 
150 cea. O.1 moie ZnO * 0.1 mole Cad 0. 
150 ec. 0,05 * Zacl ge) .O5 " Cacds 0. 


It is readily seen that the above chemical treatment was of 
iittle vaiue as an aid in increasing the demulsification number. 
The abeve trestment does by no mesns exhaust the chemical proe 
cesses through which an ofi may be put, but the lack of satisfacte]| 
ory results tended to discourage furtaer treatment in this manner. | 

¥roa the behavior of the oil in the various treatments it 
was suspected that the unsaturation in the 011 was a factor that 
was causing seme of the emulsification. With this theory in view 
it was undertaken to prove or disprove it. 

An iedine number by the Hanus method was run on the oil and 
a value of 1.64% obtained. in determining the structure of the 
cenpounds in the oil, it was found that the oi1 gave a tormalite 
number of 97, which is to say that the oil is composed chiefly 


of cyolia hydrocarbons. 


aa to the effect of eyclic hydrocarbons on emulsification, 


Lue demulsification nunhber before their removal was zero, and 
after their removel 25. ‘vidently the cyclic hydrocarbons were 
not @nausing the tmuble. 

In an attempt to saturate the oil with hydrogen, organise 
methods were used ot first. Two hundred cc. of the oi] was 
brominsted and then treated with azine and hydrochloric acid. 
After washing with dilute elkali until neutral it gave a number 
of 1200. The oi1 layer contained seme water but it is readiiy 
seen that a wrest edvance has been made. 

in another method 290 es. of oil was brominated and then 
treated with 200 ec. af sicohol « 30. gr. Zine dust « 100 ec. 
of one-cightieth mole of Cus0,. Jeshing wits alkali and neutralie 


izing and taking a nuaber on the o121, it aave a number of 1560 


out af 2 possible 1620. YThe ofl contained but little water and 
cleared up completely in 2 few minutes. for fear inet seme of 
the reagents were responsible for the results, a streight hydroe 
genation was made. 

the nickel catalyst was prepared '13' by dissolving pure 
nickel in dilute nitric acid, making a syrupy solution by adding 
suger and drovping upon a bot plate. This gave e voluminous 
nickel oxide. Wive grems of this catalyst wes added to 300 ce. 
of oil, the teupersture was kent at 260° ¢, and 2 stream of hy- 


dregen was passed through the oil for 2 hours with constant 
agitetion. After filtering through Fuller's emrth the oil gave 
& munber of 1500, thie means that the oil is 96.5% demulsifiable. 


‘The dedine nuaber wes reduced from 1.604% to 0.40%. 


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Applying the same method the resulta were not so satise 
factory. Polarine No. @ was compounded with biowm rape seed 
oil in the proportion of 34% Polarine te 16% rape oi1. ‘he 
iedine nuuber of this oil was 3.45%, and its denuulsification 
number was 0. Sy hydrogenating for two hours by the ahove 
method the denulsification number was raised to a value of 1500, 
put the o11 contained « ¢onsiderable quantity of water. Jevere 
tuielesa, the compounded oii was materially neiped from a demle 
sification standpoint. Physically neither oi1 was changed to 
any grent oxtent. 

Discussion 

from the foregoing work ene mey readily foretell just 
whet will heppen if an e@il that contains soluble groups, or has 
beer compounded witn a fatty acid 18 agitated wits water for 
a few minutes. ven an oil thet has not been compounded ane 
that theoretically should contain no seluble groups ean be 
entleified. This may be cue to an electrical caarge on the 
particle, but seme of the euulsions formed in this work could 
not be broken up by acding more of toe externul phase, which 
seldone fails to break up emulsions of tnis type. This leads 
one to attribute the cause to some other factor. And this 
work has established that factor ss unsaturation. 

it is a fairly weli established fact that eyclic hydroe 


garbons with a small percentage of unsaturetion make the best 
Lubricants. '13* One of the theories advanced for co«wpo unde 


ing cils with fatty acids is that the fatty acid reecste with 
the besring metal and holds tie cil in plece. Metner there 


is a reaction or not the fetty acid enters the space around 


emma alesse yada 


pt ime remem 


Se A, a anole a 


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the eryatels of the benring and this tends to hold the nydro- 
carbon enc of the oil up so that the bearing runs on a film of 
this oil. Just how this theory applies to = satraight chain 
mingral oil, or oils composed chiefly of cyclic hydrocarbons 
with = sraall amount cf unsaturation, is beyond tne sesope of this 
work, However, it is commeniy known thet oils with a small pere 
centege of unsaturetion are better as Lubricants than oiis that 
are saturated. 

Granted thet a small percentage of unsaturation in an oi} 


causes the oil to function better asx a iubricant, just how much 


can this percentage he reduced bevore the vaiue of the cil as 

a lubricant is affected? “Shis question arises directiy es a 
result of the work on this problem. in resucing tue percent of 
unsaturution in an oil by hydrogenation the visecsity is ine 
creased in prozortion to the amount that the percentage of une 
saturation is reduced. This work shows that hydrogenation also 
increases the denuleification number, A natural question would 
arise as to how much hydrogenation it weuld take to reise the 
demtlesification number.to ea satisfactory value end how this 
would @ffect the viscosity, or lubricating power in general. 

On the Polarine Ne. 2 the unsaturation wes reduced from 1.64% 
to 0.40%, the demuleifieation nwuber raised from Bere to 96.54, 
and the viscosity was not materially changed. Thiea tends to 
show that enough hydrogenation to wake the 641 safe from an 
emulgification standpoint would net affect tue Vivpoosity or the 
Luoriesting value. it is know that the viscosity is not 
materially changed, vut the iubvvricating value before and after 


treatment was not worked out. rom tiie appearance of tne oil, 


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“48 


one wieght advance the opinion that the lubricating value waa 
not changed, but this is oniy an epinion. To answer the quese 
tion fully, the lubricating power verore and after treatment 
would have to be wrked out, then the full value of this work 


would be KG WM 


Bibliography 


Jourmals 

"1% Jour il & waiter ak 42 det 

tar de Phys ae 

"3' Lewis, KolieLaeZe. 

t4) 2, Phya, Chieins , 73 

151 ange hem. + 9 

16) ) (1932), 

71 lid 

Ot has, Be 1914 179. 

‘Ot Thid., 34 (1899), 
‘10% 3, Chem, Soa,, 92 (3807), 2001. 
"11" Kolloides., 7 (1920), 

#32) J. Phys. Chem, 20 (1936), 407. 
*a5* Pree. Nats Acads OLe » 3 Goins. 25d. 
2921), 24, : Pe 287 . 


"14" Ger Pat., (260,000), 1921. 

415" them. ind,, 4a ( 

“26% Du. HOt. mth ind, 12 (29 120) are 

t17' J. Phya. Chen, 49: 275, 5435 etd 207 As 


Beeks 
ixeminetion of Pretrolewn. « Heanor & Padgett. 
The Petrolew: Industry. « Bacon & ilamor, 


UNIVERSITY OF ILLINOIS-URBANA 


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